CN115121255A - Preparation method of nickel-based catalyst, nickel-based catalyst and application of nickel-based catalyst - Google Patents
Preparation method of nickel-based catalyst, nickel-based catalyst and application of nickel-based catalyst Download PDFInfo
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- CN115121255A CN115121255A CN202210909883.2A CN202210909883A CN115121255A CN 115121255 A CN115121255 A CN 115121255A CN 202210909883 A CN202210909883 A CN 202210909883A CN 115121255 A CN115121255 A CN 115121255A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention provides a preparation method of a nickel-based catalyst, the nickel-based catalyst and application thereof. The preparation method of the nickel-based catalyst comprises the following steps: 1) for silicon dioxide and Ni (NO) 3 ) 2 ·6H 2 Performing ball milling treatment on the mixture of O to obtain a ball-milled product; 2) calcining the ball-milling product to obtain a catalyst precursor; 3) and reducing the catalyst precursor to obtain the nickel-based catalyst. In the nickel-based catalyst prepared by the preparation method of the nickel-based catalyst, the silicon dioxide carrier has high density, and the dispersion degree of the nickel simple substance on the surface of the silicon dioxide carrier is high, so that the nickel-based catalyst has excellent carbon deposition resistance and sintering resistance.
Description
Technical Field
The invention relates to the technical field of environmental protection, and particularly relates to a preparation method of a nickel-based catalyst, the nickel-based catalyst and application thereof.
Background
With the increasing social demands, the global energy crisis and the environmental crisis such as the greenhouse effect are getting more and more serious, so that the search for suitable renewable energy sources is forcedThe eyebrow and eyelash can be cleaned. At present, the utilization of biomass as renewable energy (biomass energy) is beneficial to relieving global energy crisis and environmental crisis, and the biomass gasification technology is one of the most promising methods for biomass energy utilization. The biomass gasification technology is a process for converting solid fuel into a combustible gas mixture through a thermochemical reaction at high temperature of 800-1000 ℃, and mainly utilizes air, oxygen or water vapor as a gasification agent. Thermochemical conversion of carbonaceous materials in biomass produces non-condensable gases (e.g., carbon monoxide, carbon dioxide, a mixture of methane and hydrogen), Volatile Organic Compounds (VOCs), tars, water vapor, H 2 S, solid residue, high-carbon solid waste (coke), and trace amounts of HCN and NH 3 And HCl. Among them, the formation of tar reduces the energy efficiency of the biomass gasification process, and tar is condensed and concentrated under low temperature conditions, easily causing clogging and pollution of downstream equipment. Therefore, the treatment of tar becomes a key problem to be solved urgently in the biomass gasification process.
Tar is mainly composed of aromatic compounds such as toluene, indene, naphthalene, and the like. The tar is currently treated by catalytic reforming, i.e. conversion of the tar into useful gas (H) using a catalyst 2 CO and CH 4 ) Thereby removing tar. The use of the catalyst in the catalytic reforming method can effectively reduce the reaction temperature, but during the catalytic reforming process, the poisoning, sintering or carbon deposition of the catalyst can easily cause the rapid deactivation of the catalyst, thereby reducing the catalytic reforming efficiency of the tar and even ending the reforming process of the tar.
Therefore, there is a need to develop catalysts that are resistant to carbon deposition and to sintering.
Disclosure of Invention
The nickel-based catalyst obtained by the preparation method provided by the invention has the advantages that the compactness of the silicon dioxide carrier is high, the dispersion degree of a nickel simple substance on the surface of the silicon dioxide carrier is high, and the nickel-based catalyst has excellent poisoning resistance, carbon deposition resistance and sintering resistance.
The nickel-based catalyst is prepared by the preparation method, so that the nickel-based catalyst has excellent poisoning resistance, carbon deposition resistance and sintering resistance.
The invention provides a tar treatment method, which comprises the step of carrying out catalytic treatment by using the nickel-based catalyst, has high catalytic treatment efficiency and can convert more tar.
The invention also provides a preparation method of the nickel-based catalyst, which comprises the following steps:
1) for silicon dioxide and Ni (NO) 3 ) 2 ·6H 2 Performing ball milling treatment on the mixture of O to obtain a ball-milled product;
2) calcining the ball-milled product to obtain a calcined product;
3) cleaning the calcined product by using a nitric acid aqueous solution to obtain a catalyst precursor;
4) and reducing the catalyst precursor to obtain the nickel-based catalyst.
The preparation method as described above, wherein the metallic nickel is contained in an amount of 0.3 to 0.6% by mass based on the total mass of the ball-milled product; and/or the presence of a gas in the gas,
the temperature of the calcination treatment is 1500-1800 ℃, the air flow rate is 150-300mL/min, and the time is 5-7 h.
The production method as described above, wherein the reduction treatment is performed using a mixed gas of hydrogen and argon;
based on the total mass of the mixed gas, the volume percentage of the hydrogen is 3-5%.
The preparation method comprises the steps of reducing at the temperature of 500-650 ℃ for 4-7 h.
The invention also provides a nickel-based catalyst, wherein the nickel-based catalyst is prepared by the preparation method.
The invention also provides a tar treatment method, which comprises the step of carrying out catalytic treatment on the tar by using the nickel-based catalyst.
The method for treating tar described above, wherein the mesh number of the nickel-based catalyst is 40 to 60 mesh.
The tar treatment method further comprises introducing a Dielectric Barrier Discharge (DBD) plasma during the catalytic treatment.
The tar processing method described above, wherein the discharge gap of the plasma is 2 to 3.5 mm; and/or the presence of a gas in the gas,
the time of the catalytic treatment is 10-40 min.
The nickel-based catalyst obtained by the preparation method provided by the invention has the advantages that the compactness of the silicon dioxide carrier is high, and the dispersion degree of the nickel simple substance on the surface of the silicon dioxide carrier is high, so that the nickel-based catalyst has excellent carbon deposition resistance and poisoning resistance and sintering resistance, and is suitable for wide popularization and application.
The nickel-based catalyst provided by the invention has the advantages that the compactness of the silicon dioxide carrier is high, and the dispersion degree of the nickel simple substance on the surface of the silicon dioxide carrier is high, so that the nickel-based catalyst has excellent poisoning resistance, carbon deposition resistance and sintering resistance, and is suitable for wide popularization and application.
The invention provides a tar treatment method, which comprises the step of carrying out catalytic treatment by using the nickel-based catalyst, has high catalytic treatment efficiency and can convert more tar.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the related art, the drawings used in the description of the embodiments of the present invention or the related art are briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is an SEM image of a nickel-based catalyst A in the present invention;
FIG. 2 is a HAADF diagram of nickel-based catalyst A of the present invention;
FIG. 3 is an SEM image of a nickel-based catalyst a in the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The first aspect of the present invention provides a method for preparing the above nickel-based catalyst, which comprises the following steps:
1) for silicon dioxide and Ni (NO) 3 ) 2 ·6H 2 Performing ball milling treatment on the mixture of O to obtain a ball-milled product;
2) calcining the ball-milling product to obtain a catalyst precursor;
3) and (4) reducing the catalyst precursor to obtain the nickel-based catalyst.
It is understood that the preparation method of the nickel-based catalyst of the present invention specifically includes: 1) for silicon dioxide and Ni (NO) 3 ) 2 ·6H 2 Ball milling the mixture of O to make the silicon dioxide and Ni (NO) 3 ) 2 ·6H 2 O is dispersed more uniformly to obtain silicon dioxide and Ni (NO) 3 ) 2 ·6H 2 O, uniformly dispersing a ball-milling product;
2) for silicon dioxide and Ni (NO) in step 1) 3 ) 2 ·6H 2 Calcining the ball-milled product with the O uniformly dispersed to obtain Ni (NO) 3 ) 2 ·6H 2 O is converted into nickel oxide, the density of the silicon dioxide is improved, and after calcination treatment, the nickel oxide is loaded on the surface of the silicon dioxide carrier to form a catalyst precursor;
3) and reducing the catalyst precursor containing nickel oxide to reduce the nickel oxide into a nickel simple substance, and loading the nickel simple substance on the surface of the silicon dioxide carrier through reduction treatment to obtain the nickel-based catalyst.
In the present invention, the step 1) further comprises mixing silica and Ni (NO) 3 ) 2 ·6H 2 Mixing O to obtain silicon dioxide and Ni (NO) 3 ) 2 ·6H 2 Mixture of O, silica and Ni (NO) 3 ) 2 ·6H 2 And placing the mixture of O in a ball mill for ball milling treatment to obtain a ball milling product. The invention is to silicon dioxide and Ni (NO) 3 ) 2 ·6H 2 O is not particularly limited, and silica and Ni (NO) commonly used in the art may be selected 3 ) 2 ·6H 2 O, e.g. silica and Ni (NO) 3 ) 2 ·6H 2 O is commercially available. In some embodiments, silica and Ni (NO) 3 ) 2 ·6H 2 The mass ratio of O is (8-10): (0.1-0.3), the rotating speed of the ball milling treatment is 400-.
And step 2) further comprises the step of placing the ball-milled product in an alumina crucible, and calcining the ball-milled product in the air atmosphere to obtain a catalyst precursor.
In some embodiments, step 2) further comprises a post-treatment comprising subjecting the calcined product to a washing treatment using an aqueous nitric acid solution to convert Ni (NO) that is not completely converted into nickel oxide 3 ) 2 ·6H 2 Dissolving the O, and then placing the product after the cleaning treatment in an oven with the temperature of 80 ℃ for drying treatment to obtain the cleaning product. In some embodiments, the concentration of the nitric acid aqueous solution is 0.4-0.7mol/L, the temperature of the cleaning treatment is room temperature, and the stirring treatment is further included in the cleaning treatment process.
Further, the post-treatment also comprises the step of sequentially grinding and screening the cleaning product according to actual requirements to obtain the catalyst precursor with a specific mesh number. In some embodiments, when the mesh number of the catalyst precursor is 40-60 meshes, the catalyst precursor can be used for catalyzing tar, the efficiency of the catalytic treatment is high, and more tar can be converted and removed.
It will be appreciated that the mesh number of the catalyst precursor is equivalent to that of the catalyst.
The preparation method of the nickel-based catalyst comprising the steps can prepare the nickel-based catalyst with high silicon dioxide density and high nickel simple substance dispersion degree, and the nickel-based catalyst has excellent poisoning resistance, carbon deposition resistance and sintering resistance and is suitable for wide popularization and application.
In some embodiments of the invention, the metallic nickel is present in an amount of 0.3 to 0.6% by mass, based on the total mass of the ball-milled product. When the mass percentage content of the metallic nickel in the ball-milled product meets the range, the dispersion of the nickel simple substance on the surface of the silicon dioxide carrier is facilitated, the dispersibility of the nickel simple substance is improved, and the catalytic activity of the nickel-based catalyst is further improved.
In the invention, the parameters of the calcination treatment can be further selected so as to ensure that the density of the silica carrier is more excellent and further improve the dispersibility of the nickel simple substance on the surface of the silica carrier. In some embodiments of the invention, the temperature of the calcination treatment is 1500-.
In some embodiments of the present invention, the reduction treatment is performed using a mixed gas of hydrogen and argon;
the volume percentage of the hydrogen is 3-5% based on the total mass of the mixed gas.
It will be appreciated that the hydrogen in the gas mixture is primarily used to reduce the nickel oxide. In the invention, the mixed gas is used for reduction treatment, so that nickel oxide can be better reduced into a nickel simple substance, and the raw material of the mixed gas is easy to obtain, thereby being beneficial to saving the production cost.
Further, the temperature and time of the reduction treatment can be specifically selected to further reduce the nickel oxide into the simple nickel substance, increase the content of the simple nickel substance in the nickel-based catalyst, and further increase the catalytic efficiency of the nickel-based catalyst, in some embodiments of the present invention, the temperature of the reduction treatment is 500-650 ℃, and the time is 4-7 h.
A second aspect of the present invention provides a nickel-based catalyst prepared by the above-described preparation method.
The nickel-based catalyst is prepared by the preparation method, so that the density of the silicon dioxide carrier is high, the dispersion degree of the nickel simple substance on the surface of the silicon dioxide carrier is high, and the nickel-based catalyst has excellent poisoning resistance, carbon deposition resistance and sintering resistance and is suitable for wide popularization and application.
The third aspect of the present invention provides a tar treatment method, comprising catalytically treating tar with the above nickel-based catalyst; or the nickel-based catalyst prepared by the preparation method of the nickel-based catalyst is used for carrying out catalytic treatment on the tar.
According to the invention, the tar is catalyzed by using the nickel-based catalyst or the nickel-based catalyst prepared by the preparation method of the nickel-based catalyst, and the used catalyst has excellent poisoning resistance, carbon deposition resistance and sintering resistance, so that the catalyst is not easy to be poisoned, carbon deposition or sintered in the catalytic treatment process, and is not easy to be inactivated, the catalytic treatment efficiency of the tar is improved, and more tar is converted. Therefore, the tar treatment method has wide application prospect in the technical field of biomass gasification, and is beneficial to relieving environmental crisis such as energy crisis and greenhouse effect.
In some embodiments of the present invention, in the tar treatment process, the mesh number of the nickel-based catalyst is 40-60 meshes, which is more beneficial to improving the tar catalytic treatment efficiency and increasing the tar removal rate.
In some embodiments of the present invention, the catalytic treatment further comprises introducing a Dielectric Barrier Discharge (DBD) plasma.
In the invention, in the process of catalytic treatment, Dielectric Barrier Discharge (DBD) plasma is introduced, and the plasma and the nickel-based catalyst are coupled for catalytic treatment, so that the catalytic treatment efficiency can be further improved, and more tar can be removed.
Furthermore, the discharge gap of the plasma can be limited, and the time of the catalytic treatment can be limited, so that the efficiency of the catalytic treatment can be further improved, and the removal rate of tar can be improved. In some embodiments of the invention, the discharge gap of the plasma is 2-3.5 mm; and/or the presence of a gas in the gas,
the time of catalytic treatment is 10-40 min.
In some embodiments, the temperature of the catalytic treatment may be 200-450 ℃, and the mass to volume ratio of the nickel-based catalyst to toluene is (0.5-1.3 g): (0.5-0.7mL), the flow rate of the carrier gas during the catalytic treatment is 100mL/min, and the volume ratio of toluene to water is (1-3): (0.5-1.3).
The technical means of the present invention will be further described below with reference to specific examples.
Example 1
The preparation method of the nickel-based catalyst a of the present embodiment includes:
1) 15g of SiO 2 And 0.3735g Ni (NO) 3 ) 2 ·6H 2 Placing the O in a ball mill for continuous ball milling for 15 hours at the rotating speed of 450r/min to obtain a ball milling product;
the mass percentage content of the metallic nickel is 0.5 wt% based on the total mass of the ball-milled product;
2) calcining the ball-milling product obtained in the step 1) in an air atmosphere;
wherein the calcining time is 6h, the calcining temperature is 1600 ℃, and the air flow rate is 200 mL/min;
3) using 0.5mol/L HNO 3 Leaching the product obtained in the step 2) with an aqueous solution to realize cleaning treatment of the product obtained in the step 2), and drying the product after cleaning treatment in an oven at 80 ℃ for 12 hours to obtain a dried product;
4) sequentially grinding and screening the dried product obtained in the step 3) to obtain powder of 40-60 meshes, thus obtaining a catalyst precursor;
5) reducing the catalyst precursor obtained in the step 4) by using a mixed gas of hydrogen and argon to obtain a nickel-based catalyst A;
wherein the temperature of the reduction treatment is 650 ℃, the volume percentage of the hydrogen is 5 percent based on the total mass of the mixed gas, the flow rate of the mixed gas is 100mL/min, and the time of the reduction treatment is 6 hours.
The nickel-based catalyst a was subjected to SEM and HAADF tests, respectively, fig. 1 is an SEM image of the nickel-based catalyst a in the present invention, and fig. 2 is an HAADF image of the nickel-based catalyst a in the present invention. As shown in fig. 1 and 2, the nickel-based catalyst a has high surface compactness and high dispersion degree of the simple nickel.
The tar treatment method of the present example includes:
mixing a nickel-based catalyst A, simulated tar, Dielectric Barrier Discharge (DBD) plasma and nitrogen, and carrying out catalytic treatment on the simulated tar;
wherein the temperature of the catalytic treatment is 300 ℃, the time is 30min, and the mass of the nickel-based catalyst A is 1 g; the flow of nitrogen is 100 mL/min; the simulated tar comprises toluene and water, wherein the volume of the toluene is 0.63mL, and the volume of the water is 1.5 mL; the discharge gap of the plasma was 2 mm.
Example 2
The preparation method of the nickel-based catalyst a of the present embodiment includes:
1) 15g of SiO 2 And 0.3735g Ni (NO) 3 ) 2 ·6H 2 Placing the O in a ball mill for continuous ball milling for 15 hours at the rotating speed of 450r/min to obtain a ball milling product;
the mass percentage content of the metallic nickel is 0.5 wt% based on the total mass of the ball-milled product;
2) calcining the ball-milled product obtained in the step 1) in an air atmosphere;
wherein the calcining time is 6h, the calcining temperature is 1600 ℃, and the air flow rate is 200 mL/min;
3) using 0.5mol/L HNO 3 Leaching the product obtained in the step 2) with an aqueous solution to realize cleaning treatment of the product obtained in the step 2), and drying the product after cleaning treatment in an oven at 80 ℃ for 12 hours to obtain a dried product;
4) sequentially grinding and screening the dried product obtained in the step 3) to obtain powder of 40-60 meshes, thus obtaining a catalyst precursor;
5) reducing the catalyst precursor obtained in the step 4) by using a mixed gas of hydrogen and argon to obtain a nickel-based catalyst A;
wherein the temperature of the reduction treatment is 650 ℃, the volume percentage of the hydrogen is 5 percent based on the total mass of the mixed gas, the flow rate of the mixed gas is 100mL/min, and the time of the reduction treatment is 6 hours.
The nickel-based catalyst a was subjected to SEM and HAADF tests, respectively, fig. 1 is an SEM image of the nickel-based catalyst a in the present invention, and fig. 2 is an HAADF image of the nickel-based catalyst a in the present invention. As shown in fig. 1 and 2, the nickel-based catalyst a has high surface compactness and high dispersion degree of the simple nickel.
The tar treatment method of the embodiment includes:
mixing a nickel-based catalyst A, simulated tar, Dielectric Barrier Discharge (DBD) plasma and nitrogen, and carrying out catalytic treatment on the simulated tar;
wherein the temperature of the catalytic treatment is 300 ℃, the time is 40min, and the mass of the nickel-based catalyst A is 1 g; the flow of nitrogen is 100 mL/min; the simulated tar comprises toluene and water, wherein the volume of the toluene is 0.63mL, and the volume of the water is 1.5 mL; the discharge gap of the plasma was 2 mm.
Comparative example 1
The nickel-based catalyst a of the comparative example was prepared by a conventional impregnation method, and the nickel-based catalyst a (Ni/SiO) 2 ) In the catalyst, the mass percentage of the metallic nickel is 2 wt%, and the nickel-based catalyst a can be obtained by commercial purchase;
the nickel-based catalyst a was subjected to SEM test, and fig. 3 is an SEM image of the nickel-based catalyst a in the present invention. As can be seen from fig. 3, the surface density of the nickel-based catalyst a is low, and the nickel simple substance is agglomerated.
The tar of this comparative example was treated in substantially the same manner as in example 1 except that nickel-based catalyst a was used in place of nickel-based catalyst a in example 1.
Comparative example 2
The tar of this comparative example was treated in substantially the same manner as in example 1, except that the nickel-based catalyst A was not used.
Comparative example 3
The tar of this comparative example was treated in substantially the same manner as in comparative example 1, except that no plasma was used.
Performance test
The liquid product was tested by GC-MS (HRGC-LRMS, QP2020, Shimadzu, Japan) auto-injection, calculated as follows:
the conversion of the tar simulant was calculated by the following formula:
wherein [ T] in Is the mole number of tar in the sample; [ T ]] out Is the moles of tar in the liquid product.
TABLE 1
| Conversion of toluene/% | |
| Example 1 | 84.9 |
| Example 2 | 84.5 |
| Comparative example 1 | 74 |
| Comparative example 2 | 63 |
| Comparative example 3 | 33.91 |
As can be seen from Table 1, the nickel-based catalyst in the examples of the present invention has high tar conversion when used for tar treatment.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the nickel-based catalyst is characterized by comprising the following steps of:
1) for silicon dioxide and Ni (NO) 3 ) 2 ·6H 2 Performing ball milling treatment on the mixture of O to obtain a ball-milled product;
2) calcining the ball-milling product to obtain a catalyst precursor;
3) and reducing the catalyst precursor to obtain the nickel-based catalyst.
2. The method according to claim 1, wherein the metallic nickel is contained in an amount of 0.3 to 0.6% by mass based on the total mass of the ball-milled product.
3. The preparation method as claimed in claim 1 or 2, characterized in that the calcination treatment temperature is 1500-1800 ℃, the air flow rate is 150-300mL/min, and the time is 5-7 h.
4. The production method according to any one of claims 1 to 3, wherein the reduction treatment is performed using a mixed gas of hydrogen and argon;
the volume percentage of the hydrogen is 3-5% based on the total mass of the mixed gas.
5. The method as claimed in claim 4, wherein the temperature of the reduction treatment is 500-650 ℃ and the time is 4-7 h.
6. A nickel-based catalyst, characterized by being prepared according to the preparation method of any one of claims 1 to 5.
7. A method for treating tar, comprising catalytically treating said tar with the nickel-based catalyst according to claim 6.
8. The method of processing tar according to claim 7, wherein the nickel-based catalyst has a mesh size of 40 to 60 mesh.
9. The method for treating tar according to claim 7 or 8, further comprising introducing dielectric barrier discharge plasma during the catalytic treatment.
10. The method for treating tar according to claim 9, wherein the discharge gap of the plasma is 2 to 3.5 mm; and/or the presence of a gas in the gas,
the time of the catalytic treatment is 10-40 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110270377A (en) * | 2019-07-01 | 2019-09-24 | 西京学院 | A kind of methane dry reforming nickel-base catalyst and its preparation method and application |
| CN112246245A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | Supported nickel-based catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110270377A (en) * | 2019-07-01 | 2019-09-24 | 西京学院 | A kind of methane dry reforming nickel-base catalyst and its preparation method and application |
| CN112246245A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | Supported nickel-based catalyst and preparation method and application thereof |
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